CN115561293A - Zinc oxide modified nano porous gold and preparation method and application thereof - Google Patents
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Abstract
The invention provides zinc oxide modified nano-porous gold and a preparation method and application thereof, wherein the preparation method of the zinc oxide modified nano-porous gold comprises the following steps: placing gold as a working electrode in a zinc salt solution, and carrying out electrochemical alloying/dealloying treatment to obtain a gold-zinc porous alloy; and carrying out heat treatment on the gold-zinc porous alloy to obtain the zinc oxide modified nano porous gold. The zinc oxide modified nano-porous gold is constructed by in-situ alloying and dealloying methods, and when the zinc oxide modified nano-porous gold is used as an electrode for an electrochemical analysis sensor, rapid and high-sensitivity monitoring on low-concentration heavy metal trivalent arsenic ions can be realized.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to zinc oxide modified nano porous gold and a preparation method and application thereof.
Background
Arsenic has a high toxicity, especially trivalent arsenic ions, which is 56 times as toxic as other arsenic ions. Trivalent arsenic is widely present in groundwater and causes various adverse effects on human beings when exposed to a trivalent arsenic environment for a long time. The trivalent arsenic limit standard reported by the world health organization is 10ppb, and the arsenic content of underground water in a plurality of regions of 20 countries exceeds the standard at present, including northwest and inner Mongolia regions of China, so that a high-sensitivity sensor is required for detection.
The electrochemical catalyst plays an important role in an electrochemical reaction system, and can accelerate electron transfer and reduce reaction activation energy. For many years, researchers have been working on developing electrochemical catalysts with high catalytic activity, such as increasing specific surface area, electrochemically active sites, or regulating mass transfer diffusion of reactants at the electrode-electrolyte interface. Among them, porous metal materials having a three-dimensional staggered network structure have attracted much attention in electrochemical catalysis due to their unique properties. The porous metal material has a better catalytic structure, and the staggered net structure can effectively promote the mass transfer and diffusion of reactants; the reticulated internal height profile structure can expose multiple crystal planes, thereby providing diverse electrochemically active sites. The zinc oxide also shows excellent performance in detecting trivalent arsenic due to the unique adsorption and catalysis effects.
At present, diversified technical means are applied to the construction of porous metal materials, such as an alloy removing method, an electrochemical deposition method, a template synthesis method and the like. The dealloying method is widely applied, and a binary or ternary alloy consisting of noble metal and active metal is usually used as an initial reactant, and the active metal is dissolved in multiple steps under the strong acid or strong alkaline condition, so that a porous structure of the noble metal is formed. The method is harsh in condition, needs strong acid and strong alkali conditions, and lacks certain controllability in the construction of the ordered porous structure. Therefore, the development of controllable and cheap nano-porous structure materials is still a great challenge and significant.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides zinc oxide modified nano-porous gold and a preparation method and application thereof.
The invention provides a preparation method of zinc oxide modified nano-porous gold, which comprises the following steps:
s1, placing gold serving as a working electrode in a zinc salt solution, and carrying out electrochemical alloying/dealloying treatment to obtain a gold-zinc porous alloy;
s2, carrying out heat treatment on the gold-zinc porous alloy to obtain the zinc oxide modified nano porous gold.
Preferably, step S1 further comprises using zinc as the auxiliary electrode and the reference electrode, respectively.
Preferably, in step S1, the gold micro-disk is placed in a zinc salt solution as a working electrode.
Compared with gold wires and the like serving as working electrodes, the gold micro-disc has higher mass transfer efficiency, reduces diffusion and convection, is beneficial to zinc loading and modification, and finally can be used for obtaining the zinc oxide modified nano-porous gold micro-disc with high surface area and uniform porous structure.
Preferably, in step S1, the zinc salt solution is a zinc salt alcohol solution;
preferably, the zinc salt is zinc chloride and the alcohol is ethylene glycol.
Preferably, the electrochemical alloying/dealloying treatment is to perform cyclic scanning on the working electrode by using linear voltammetry, and the completion of cathode scanning is taken as the end of the last cyclic scanning;
in the invention, the surface of gold is alloyed and dealloyed by cyclic voltammetry, thus preparing the nano-porous gold-zinc alloy: in cathode potential scanning, zinc ions can be reduced and electrodeposited on the surface of a gold working electrode, an AuZn alloy is formed on the surface of the gold working electrode, in subsequent anode potential scanning, reduced zinc is gradually oxidized to form zinc ions, the zinc ions are dissolved and diffused into electrolyte, zinc migrates on the surface of the gold working electrode to cause synchronous migration of gold atoms, the electrodeposition, migration and dissolution of the zinc ions can be repeated in the subsequent cathode reduction/anode oxidation circulation process, and the gold with a three-dimensional nano porous structure, namely the nano porous gold is prepared, the specific surface roughness volume of the gold is greatly increased, and the nano porous gold has a synergistic sensitization mechanism of noble metal nano particles and the porous nano structure, and has very high current density and charge transfer electron speed when being used as an electrode; meanwhile, the invention also further stops the last cycle before the anode scanning is started, namely stops the cycle when the potential is swept to 0V before the anode scanning is started, so that the zinc deposited on the porous nano gold can not be dissolved out again, and the nano porous gold-zinc alloy is prepared.
The nano-porous gold-zinc alloy is subjected to high-temperature heat treatment to obtain zinc oxide modified nano-porous gold, and the nano-porous gold has excellent performance of analyzing ions with silk quantity, so that the detection of toxic heavy metal trivalent arsenic ions can be realized.
Preferably, the voltage of the cyclic scanning is-0.8-1.8V, the speed of the cyclic scanning is 8-12mV/s, the temperature of the cyclic scanning is 90-130 ℃, and the number of the cyclic scanning is 2-20;
preferably, the potential of the cathode scan is-0.8-0V.
According to the invention, by controlling parameters such as cyclic voltammetry, cycle time and the like, the specific surface area of the obtained zinc oxide modified nano-porous gold is effectively changed, and the electrochemical sensitive response of a trace analyte is improved.
Preferably, before the step S1, cyclic scanning is performed on the working electrode by using linear voltammetry, so as to activate the gold working electrode;
preferably, the electrolyte of the cyclic scanning is sulfuric acid solution, the voltage of the cyclic scanning is 0-1.5V, the speed of the cyclic scanning is 40-60mV/s, and the number of the cyclic scanning is 4-6.
Preferably, in step S2, the heat treatment temperature is 130-170 ℃ and the time is 80-160min;
preferably, the heat treatment is performed in an air atmosphere.
The invention provides zinc oxide modified nano-porous gold which is prepared by the preparation method.
The invention provides an electrochemical catalyst which comprises the zinc oxide modified nano-porous gold.
The invention also provides an electrochemical analysis sensor which comprises an electrochemical sensing electrode constructed by the zinc oxide modified nano-porous gold;
preferably, the electrochemical analysis and analysis sensor is used for detecting toxic heavy metal ions;
preferably, the toxic heavy metal ion is a trivalent arsenic ion.
The invention processes the working electrode of gold by an electrochemical method, and prepares zinc oxide modified nano-porous gold by a cyclic scanning technology; specifically, the zinc oxide modified nano-porous gold is obtained by carrying out high-temperature heat treatment on the gold-zinc porous alloy with active zinc elements by an in-situ reduction method.
The zinc oxide modified nano-porous gold is used as an electrochemical sensing electrode, and can be effectively applied to detection of toxic heavy metal trivalent arsenic ions. Tests show that the zinc oxide modified nanoporous gold phase has significantly improved electrochemical detection performance on heavy metal trivalent arsenic ions compared with bare gold with a smooth surface. Meanwhile, the specific surface area of the gold is obviously improved by the electrochemical treatment technology, and the roughness of the gold is obviously increased compared with that of bare gold with a smooth surface.
The zinc oxide modified nano-porous gold prepared by electrochemistry and an in-situ reduction oxidation method has high catalytic activity and large specific surface area, realizes high-sensitivity detection on heavy metal trivalent arsenic ions, and effectively solves the problems of difficult electrochemical capture and low sensitivity on the trivalent arsenic ions.
Drawings
FIG. 1 is an SEM image of a gold micro-disk and zinc oxide modified nanoporous gold prepared according to an embodiment of the invention: (a) Is SEM picture of gold micro-disc, (b) is SEM picture of zinc oxide modified nano-porous gold electrode;
FIG. 2 is an XRD diagram of gold micro-disk, gold-zinc porous alloy and zinc oxide modified nano-porous gold prepared by the method of the present invention;
FIG. 3 is a cyclic voltammetry curve of the gold-zinc porous alloy prepared under different cyclic scanning cycles in sulfuric acid according to the present invention;
fig. 4 is a sensitivity detection diagram of trivalent arsenic ions when zinc oxide modified nanoporous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor: (a) When the zinc oxide modified nano-porous gold is used for an electrochemical analysis sensor, the square wave dissolution curve of trivalent arsenic ions is obtained; (b) is a linear fit of figure a;
FIG. 5 is a graph showing the sensitivity of nanoporous gold prepared according to the comparative example of the present invention to trivalent arsenic ions when used in an electrochemical analytical sensor: (a) The square wave dissolution curve of the nano porous gold to trivalent arsenic ions when the nano porous gold is used for an electrochemical analysis sensor; (b) is a linear fit of figure a;
fig. 6 is a repeated detection chart of 100ppb trivalent arsenic ion when the zinc oxide modified nano-porous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor: (a) The method is a square wave dissolution curve and a peak current line graph of zinc oxide modified nano-porous gold during repeated detection of 100ppb trivalent arsenic ions; (b) Detecting a current response histogram of 100ppb trivalent arsenic ions for zinc oxide modified nanoporous gold prepared for different batches;
fig. 7 is an anti-interference performance test chart for detecting trivalent arsenic ions when the zinc oxide modified nanoporous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Examples
A preparation method of zinc oxide modified nano-porous gold comprises the following steps:
(1) Taking a gold wire with the diameter of 25 mu m, the length of 30mm and a smooth surface, placing the gold wire into a high borosilicate glass tube with one end being condensed into a small hole at high temperature, penetrating one end of the gold wire into the small hole, enabling the tail end of the gold wire to be tightly attached to the small hole and carrying out high-temperature treatment, enabling the tail end of the gold wire to be sealed at the opening of the glass tube, carrying out vacuum treatment on the high borosilicate glass tube, sealing one part of the gold wire in the glass tube in a high-temperature atmosphere, and polishing the opening of the glass tube to be disc-shaped by using a grinding wheel so as to enable the surface of the gold micro disc to be smooth; another copper wire is taken, one end of the copper wire is wrapped with silver paste, the end wrapped with the silver paste penetrates into the glass tube and is connected with one end of the gold wire which is not sealed in the glass tube, the glass tube is placed in an oven to be dried, the dried copper wire is taken out to be measured whether the gold wire is conductive or not by using a universal meter, after the conductivity is measured to be good, the port of the glass tube is sealed by using AB glue, and after the gold wire is naturally dried, a gold micro disc is prepared;
(2) Placing 5mL of 0.1M sulfuric acid solution in an electrolytic cell, introducing nitrogen for 15min, and discharging air in the sulfuric acid solution; taking the gold micro disc prepared in the step (1) as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, placing the three electrodes in the sulfuric acid solution, connecting the three electrodes to an electrochemical workstation, and performing cyclic scanning by adopting a three-electrode cyclic voltammetry method to activate the working electrode, wherein the initial voltage is 0V, the final voltage is 1.5V, the scanning speed is 50mV/s, and the activated gold micro disc is obtained after 5 cycles of cyclic scanning;
(3) Putting 1.022g of zinc chloride and 5mL of ethylene glycol into an electrolytic cell, and performing ultrasonic treatment until the zinc chloride is dissolved to form a transparent clear solution to obtain a zinc salt solution; respectively polishing the zinc sheet and the zinc rod to be bright so as to remove surface oxidation films, and ultrasonically cleaning in ethanol for 5min to obtain the cleaned zinc sheet and the cleaned zinc rod; soaking the zinc salt solution in silicon oil, heating to 110 ℃, taking the gold micro disc subjected to activation treatment in the step (2) as a working electrode, taking a cleaned zinc rod as a counter electrode, taking a cleaned zinc sheet as a counter electrode, taking a zinc rod as a reference electrode, placing the three electrodes in the zinc salt solution, connecting the three electrodes to an electrochemical workstation, performing cyclic scanning by adopting a three-electrode cyclic voltammetry method, stopping the cyclic scanning after the cathode scanning is finished at a 10 th cycle, taking out the working electrode, and washing the organic solvent remained on the surface by absolute ethyl alcohol to obtain the gold-zinc porous alloy;
(4) And (4) carrying out heat treatment on the gold-zinc porous alloy prepared in the step (3) at 150 ℃ for 2h in an air atmosphere, and cooling to room temperature to obtain the zinc oxide modified nano porous gold.
Scanning electron microscope detection is performed on the gold micro-discs and the zinc oxide modified nanoporous gold prepared in the example, and the result is shown in fig. 1, and fig. 1 is an SEM image of the gold micro-discs and the zinc oxide modified nanoporous gold prepared in the example. Referring to fig. 1, after the electrochemical alloying/dealloying treatment, the gold micro-disc surface with smooth surface forms a uniform nano-porous structure.
X-ray powder diffraction analysis was performed on the gold micro-disk and the zinc oxide-modified nanoporous gold obtained in example, and the result is shown in fig. 2, where fig. 2 is an XRD chart of the gold micro-disk, the gold-zinc porous alloy and the zinc oxide-modified nanoporous gold obtained in example. Fig. 2 shows XRD patterns of gold micro-disk (NPG), gold zinc porous alloy (Zn/NPG), and zinc oxide modified nanoporous gold (ZnO/NPG), assigning strong peaks at 2 θ =38.2, 44.4, 64.5, 77.5, and 81.7 ° to the (111), (200), (220), (311), and (221) planes of face centered cubic Au (JCPDS No. 04-0784). Referring to fig. 2, it can be seen that new peaks around 28.4, 40.6, 50.2, 58.7, 66.5 and 73.8 ° are clearly present in Zn/NPG obtained at 0.0V during the electrochemical alloying/dealloying process; when further calcined under an air atmosphere, additional peaks at 31.7, 34.4, 36.2, 47.5, 56.6, 62.8, 67.9 and 69.1 ° were clearly observed, which fit into the (102), (110), (103), (112) and (201) planes of (100), (002), (101) hexagonal structure ZnO, compared to NPG; it is known that zinc oxide-modified nanoporous gold has both diffraction characteristic peaks of gold and zinc oxide.
Except that in the step (3) of the example, only 0, 2, 5, 15 and 20 cycles of cyclic scanning were performed, the gold-zinc porous alloy was obtained by cyclic scanning for 0, 2, 5, 15 and 20 cycles, respectively, and the gold-zinc porous alloy was obtained by cyclic scanning for 10 cycles in the example.
Respectively taking the gold-zinc porous alloy prepared after the cyclic scanning for 0, 2, 5, 10, 15 and 20 circles as working electrodes, in a 0.1M sulfuric acid solution, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, connecting an electrochemical workstation, and performing cyclic scanning by adopting a three-electrode cyclic voltammetry method until a stable cyclic voltammetry curve is obtained, wherein the initial voltage is 0V, the final voltage is 1.5V, and the scanning rate is 50mV/s; the results are shown in fig. 3, and fig. 3 is a cyclic voltammogram of the gold-zinc porous alloy prepared by the invention in sulfuric acid under different cyclic scanning cycles.
Referring to fig. 3, it can be seen that oxidation and reduction peaks of the obtained gold-zinc porous alloy are significantly increased after 2 cycles of the electrochemical alloying/dealloying process compared to the gold micro-disk (cycle scan 0), and a wide oxidation peak of gold and sharp oxide reduction peaks around 1.3V and 0.9V, which are derived from the formation of gold oxide and the reduction of gold oxide, can be clearly observed. In addition, after 5 cycles of electrochemical alloying/dealloying treatment, oxidation and reduction peaks of gold-zinc porous alloy (NPG- μ E) significantly increased as the electric double layer was enlarged; but increasing the number of cycles from 10 to 20, the reduction peak of the gold-zinc porous alloy for the gold oxide was almost stable or slightly decreased.
Comparative example
A preparation method of nano-porous gold comprises the following steps:
(1) Taking a gold wire with the diameter of 25 mu m, the length of 30mm and a smooth surface, placing the gold wire into a high borosilicate glass tube with one end being condensed into a small hole at high temperature, penetrating one end of the gold wire into the small hole, enabling the tail end of the gold wire to be tightly attached to the small hole and carrying out high-temperature treatment, enabling the tail end of the gold wire to be sealed at the opening of the glass tube, carrying out vacuum treatment on the high borosilicate glass tube, sealing one part of the gold wire in the glass tube in a high-temperature atmosphere, and polishing the opening of the glass tube to be disc-shaped by using a grinding wheel so as to enable the surface of the gold micro disc to be smooth; another copper wire is taken, one end of the copper wire is wrapped with silver paste, the end wrapped with the silver paste is penetrated into a glass tube and is connected with one end of an unsealed gold wire in the glass tube, the glass tube is placed in an oven to be dried, the dried copper wire is taken out, a universal meter is used for measuring whether the gold wire is conductive or not, after the conductivity is measured to be good, AB glue is used for sealing the port of the glass tube, and after the gold wire is naturally dried, a gold micro disc is prepared;
(2) Placing 5mL of 0.1M sulfuric acid solution in an electrolytic cell, introducing nitrogen for 15min, and discharging air in the sulfuric acid solution; taking the gold micro disc prepared in the step (1) as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, placing the three electrodes in the sulfuric acid solution, connecting the three electrodes to an electrochemical workstation, and performing cyclic scanning by adopting a three-electrode cyclic voltammetry method to activate the working electrode, wherein the initial voltage is 0V, the final voltage is 1.5V, the scanning speed is 50mV/s, and the activated gold micro disc is obtained after 5 cycles of cyclic scanning;
(3) Putting 1.022g of zinc chloride and 5mL of ethylene glycol into an electrolytic cell, and performing ultrasonic treatment until the zinc chloride is dissolved to form a transparent clear solution to obtain a zinc salt solution; respectively polishing the zinc sheet and the zinc rod to be bright so as to remove surface oxide films, and ultrasonically cleaning in ethanol for 5min to obtain the cleaned zinc sheet and zinc rod; and (2) soaking the zinc salt solution in silicon oil, heating to 110 ℃, taking the gold micro disc subjected to activation treatment in the step (2) as a working electrode, taking a cleaned zinc rod as a counter electrode, taking a cleaned zinc sheet as a counter electrode, taking the zinc rod as a reference electrode, placing the three electrodes in the zinc salt solution, connecting the three electrodes to an electrochemical workstation, performing cyclic scanning by adopting a three-electrode cyclic voltammetry method, taking out the working electrode, washing the organic solvent remained on the surface by absolute ethyl alcohol, and drying to obtain the nano porous gold.
Test example:
the zinc oxide modified nano-porous gold prepared in the example is used As a working electrode to carry out electrochemical analysis and test, a Pt wire and Ag/AgCl are respectively used As a counter electrode and a reference electrode to form a three-electrode test system, 0.1M phosphate buffer solution (pH is 5) is used As electrolyte, and toxic heavy metal trivalent arsenic ions (As) 3+ ) Is the analyte. Before testing, inert nitrogen is introduced into the electrolyte for 20min to remove oxygen dissolved in the electrolyte, a wave anode stripping voltammetry is used as an analysis method, and the experimental conditions are as follows: the deposition potential and time are-0.4V and 120s; the desorption potential and time were 0.6V,150s; the step voltage is 4mV; amplitude of 25mV; the frequency is 25Hz; scanning the electrolyte; adding trivalent arsenic solution with concentration of 1-260ppb, stirring the electrolyte uniformly, scanning under the same condition, and obtaining the scanning result shown in the figureFig. 4 is a diagram showing a sensitivity detection chart of trivalent arsenic ions when the zinc oxide modified nanoporous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor: (a) When the zinc oxide modified nano-porous gold is used for an electrochemical analysis sensor, a square wave dissolution curve of trivalent arsenic ions is obtained; and (b) is a linear fit of the graph a.
Referring to FIG. 4, it can be seen that the zinc oxide modified nanoporous gold prepared in the embodiments of the present invention has-0.1V vs. As 3+ Shows stronger electrochemical oxidation behavior.
Similarly, the nanoporous gold prepared in the comparative example was used as a working electrode to perform electrochemical analysis, and the test conditions were the same as above, except that trivalent arsenic solution with concentration of 1-150ppb was added, and scanning was performed under the same conditions, and the scanning results are shown in fig. 5, and fig. 5 is a sensitivity detection chart of the nanoporous gold prepared in the comparative example of the present invention on trivalent arsenic ions when used in an electrochemical analysis sensor: (a) The square wave dissolution curve of the nano porous gold to trivalent arsenic ions when the nano porous gold is used for an electrochemical analysis sensor; and (b) is a linear fit of the graph a.
Referring to fig. 5, it can be seen that the zinc oxide-modified nanoporous gold microdisc electrode pair prepared in the example was As compared to the nanoporous gold microdisc electrode prepared in the comparative example 3+ The electrochemical response sensitivity of the zinc oxide nano-porous gold is improved by 6.3 times, and the zinc oxide modified nano-porous gold has higher electrocatalytic activity.
For 100ppb of As under the same conditions 3+ The result of the repeatability test is shown in fig. 6, and fig. 6 is a diagram of the repeatability test of 100ppb trivalent arsenic ions when the zinc oxide modified nanoporous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor: (a) The method is a square wave dissolution curve and a peak current line graph of zinc oxide modified nano-porous gold during repeated detection of 100ppb trivalent arsenic ions; (b) And detecting a current response histogram of 100ppb trivalent arsenic ions for the zinc oxide modified nano-porous gold prepared in different batches.
Referring to fig. 6, it can be seen that the zinc oxide modified nanoporous gold prepared by the embodiment of the invention shows better repeatability.
When the zinc oxide modified nano-porous gold prepared by the embodiment of the invention is used for detecting 100ppb trivalent arsenic ions, anti-interference ions with the concentration of 5 times are added, the detection result is shown in fig. 7, and fig. 7 is an anti-interference performance test chart for detecting trivalent arsenic ions when the zinc oxide modified nano-porous gold prepared by the embodiment of the invention is used in an electrochemical analysis sensor.
Referring to fig. 7, the zinc oxide modified nano-porous gold prepared by the embodiment of the invention has better anti-interference performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of zinc oxide modified nano-porous gold is characterized by comprising the following steps:
s1, placing gold serving as a working electrode in a zinc salt solution, and carrying out electrochemical alloying/dealloying treatment to obtain a gold-zinc porous alloy;
s2, carrying out heat treatment on the gold-zinc porous alloy to obtain the zinc oxide modified nano porous gold.
2. The method for preparing zinc oxide modified nanoporous gold according to claim 1, wherein the step S1 further comprises using zinc as an auxiliary electrode and a reference electrode, respectively.
3. The method for preparing zinc oxide modified nanoporous gold according to claim 1 or 2, wherein in step S1, the gold micro-disk is placed in a zinc salt solution as a working electrode.
4. The method for preparing zinc oxide modified nanoporous gold according to any one of claims 1 to 3, wherein in step S1, the zinc salt solution is a zinc salt alcohol solution, the zinc salt is preferably zinc chloride, and the alcohol is preferably ethylene glycol.
5. The method for preparing zinc oxide modified nanoporous gold according to any one of claims 1 to 4, wherein in step S1, the electrochemical alloying/dealloying process is performed by cyclic scanning of the working electrode by using linear voltammetry, and completion of cathode scanning is taken as the end of the last cyclic scanning;
preferably, the voltage of the cyclic scanning is-0.8-1.8V, the speed of the cyclic scanning is 8-12mV/s, the temperature of the cyclic scanning is 90-130 ℃, and the number of cycles of the cyclic scanning is 2-20;
preferably, the voltage of the cathode scan is-0.8-0V.
6. The preparation method of the zinc oxide modified nanoporous gold according to any one of the claims 1 to 5, wherein before the step S1, the method further comprises the steps of performing cyclic scanning on the working electrode by using a linear voltammetry method to activate the working electrode of gold;
preferably, the electrolyte of the circular scanning is sulfuric acid solution, the voltage of the circular scanning is 0-1.5V, the speed of the circular scanning is 40-60mV/s, and the times of the circular scanning are 4-6.
7. The method for preparing zinc oxide modified nanoporous gold according to any one of claims 1 to 6, wherein in step S2, the heat treatment temperature is 130 to 170 ℃ and the time is 80 to 160min;
preferably, the heat treatment is performed in an air atmosphere.
8. The zinc oxide modified nanoporous gold prepared by the preparation method of any one of claims 1 to 7.
9. An electrochemical catalyst comprising the zinc oxide-modified nanoporous gold of claim 8.
10. An electrochemical analytical sensor, which comprises an electrochemical sensing electrode constructed by zinc oxide modified nanoporous gold according to claim 8;
preferably, the electrochemical analysis sensor is used for detecting toxic heavy metal ions;
preferably, the toxic heavy metal ion is a trivalent arsenic ion.
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| CN113699547A (en) * | 2021-08-06 | 2021-11-26 | 昆明理工大学 | Preparation method and application of porous alloy electrode |
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| CN113699547A (en) * | 2021-08-06 | 2021-11-26 | 昆明理工大学 | Preparation method and application of porous alloy electrode |
| CN113699547B (en) * | 2021-08-06 | 2023-07-21 | 昆明理工大学 | Preparation method and application of porous alloy electrode |
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